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Supplemental Materials Fuel Specific Influences on the Composition of Reaction Intermediates in Premixed Flames of Three C 5 H 10 O 2 Ester Isomers Bin Yang, Charles K. Westbrook, Terrill A. Cool, Nils Hansen and Katharina Kohse Höinghaus Supplemental Material-Part 1 (pdf file): Figures S1-S3 and Table S1-S4 Figure S1: PIE spectra for mass 30 and 40 in the three ester flames Figure S2: C 4 species detected in the three ester flames, as well as the modeling results for C 4 H 6 Figure S3: Mole fraction profiles for oxygenated intermediates detected in the three ester flames Table S1: Photon energies used and photoionization cross-sections for detected flame species Table S2: Kinetic reaction mechanism for ethyl propanoate. Table S3: Methyl isobutanoate mechanism, including submechanism for methyl methacrylate Table S4: Rate expressions for H atom abstraction reactions by OH, H, and HO2 radicals in functional groups of importance in the present study Supplemental Material-Part 2 (Excel file): Table S5 Measured temperautre profiles and measured mole fractions for the three ester flames are provided in the file: Supp2.xlsx. 1

Fig. S1. PIE spectra for mass 30 and 40 in the three ester flames. Relative Ion Signal PIE for m/z=30 MB Flame MIB Flame EP Flame Ethane IE=11.52 ev Formaldehyde IE=10.88 ev a PIE for m/z=40 MB Flame MIB Flame EP Flame 30% Allene+ 70% Propyne Allene IE=9.69 ev Propyne IE=10.33 ev b 10.8 11.2 11.6 12.0 9.2 9.6 10.0 10.4 10.8 Photon Energy (ev) Fig. S2. C 4 species detected in the three ester flames, as well as the modeling results for C 4 H 6. 0.0003 0.0002 MB MIB EP C 4 H 2 Exp C 4 H 4 Exp C 4 H 6 Exp 0.0003 0.0002 Mole Fractions 0.0001 0.0000 0.0001 C 4 H 6 Mod 0.0001 0.0000 0.0001 0.0002 0.0002 0.0003 0 2 4 6 0 2 4 6 Distance from Burner (mm) 2 0.0003 0 2 4 6 8

Fig. S3. Mole fraction profiles for oxygenated intermediates detected in the three ester flames. 0.0010 MB MIB EP 0.0010 CH 2 CHOH CH 3 CHCO / C 4 H 8 C 2 H 5 CHCO / (CH 3 ) 2 CCO 0.0005 0.0005 Mole Fraction 0.0000 0.0010 C 2 H 4 O 2 C 3 H 6 O 2 C 4 H 6 O 2 C 4 H 8 O 2 0.0000 0.0010 C 5 H 8 O 2 C 6 H 12 O 2 0.0005 0.0005 0.0000 0 2 4 6 0 2 4 6 Distance from Burner (mm) 0.0000 0 2 4 6 8 3

Table S1. Photon energies used (E) and photoionization cross-sections (σ(e)) for detected flame species. M/z Formula Species E IP σ(e) ev ev Mb [Ref] 2 H 2 Hydrogen 16.2 15.43 X a 15 CH 3 Methyl radical 11.5 9.84 7 [1] 16 CH 4 Methane 13.2 12.61 5 [2] 18 H 2 O Water 13.2 12.62 X a 26 C 2 H 2 Acetylene 13.2 11.4 39 [3] 28 CO Carbon Monoxide 14.35 14.01 X a 28 C 2 H 4 Ethylene 11.5 10.51 8 [3] 30 CH 2 O Formaldehyde 11.5 10.88 10.2 [3] 30 C 2 H 6 Ethane 12.3 11.52 13.3 [2] 32 O 2 Oxygen 13.2 12.07 X a 32 CH 3 OH Methanol 11.5 10.84 9.6 [3] 39 C 3 H 3 Propargyl radical 10.0 8.67 8.8 [4] 40 Ar Argon 16.2 15.76 X a 40 C 3 H 4 Allene 10.0 9.69 6.6 [5] 40 C 3 H 4 Propyne 11.5 10.36 42.1 [5] 41 C 3 H 5 Allyl radical 10.0 8.18 6.2 [6] 42 C 3 H 6 Propene 10.0 9.73 8.5 [7] 42 C 2 H 2 O Ketene 10.0 9.62 21 [8 44 CO 2 Carbon Dinoxide 14.35 13.78 X a 44 C 2 H 4 O Ethenol 10.0 9.33 6.4 [5] 44 C 2 H 4 O Acetaldehyde 11.5 10.23 9.7 [5] 50 C 4 H 2 Diacetylene 11.5 10.17 34 [3] 52 C 4 H 4 Vinylacetylene 11.5 9.58 39 [3] 54 C 4 H 6 1,3-Butadiene 11.5 9.07 24 [7] 56 C 4 H 8 Cis-2-Butene 10.0 9.09 9.10 [2] 56 C 3 H 4 O Methyl Ketene 10.0 8.95 20 Est b 58 C 3 H 6 O Acetone 10.5 9.70 11.2 [3] 60 C 2 H 4 O 2 Acetic Acid 11.5 10.65 19.4 [8] 60 C 2 H 4 O 2 Methyl formate 11.5 10.83 7.64 [9] 70 C 4 H 6 O Ethyl ketene 9.7 8.80 20 EST b 70 C 4 H 6 O Dimehtyl ketene 9.7 8.38 20 EST b 74 C 3 H 6 O 2 Propanoic acid 11.5 10.44 19.4 EST b 86 C 4 H 6 O 2 Methyl propenoate 10.5 10.0 2.28 [9] 4

86 C 4 H 6 O 2 Vinyl acetate 10.5 9.31 18.0 [9] 88 C 4 H 8 O 2 Methyl propanoate 10.5 10.06 7.9 [9] 88 C 4 H 8 O 2 Ethyl acetate 10.5 9.95 6.18 [9] 100 C 5 H 8 O 2 Methyl crotonate 10.5 9.7 8.5 [9] 100 C 5 H 8 O 2 Ethyl propenoate 10.5 9.9 4.5 [9] 102 C 5 H 10 O 2 Methyl butanoate 10.5 9.85 3.4 [9] 102 C 5 H 10 O 2 Methyl isobutynate 10.5 9.74 16.9 [9] 102 C 5 H 10 O 2 Ethyl propanoate 10.5 9.85 9.68 [9] 116 C 6 H 12 O 2 10.5 10 Est b a) X in the table indicates that photoionization cross sections are not used for the mole fraction determination; b) Est in the table indicates that the cross section data is estimated. References: [1] C. A. Taatjes, D. L. Osborn, T. M. Selby, G. Meloni, H. Fan and S. T. Pratt, J. Phys. Chem. A, 2008, 112, 9336. [2] J. Wang, B. Yang, T. A. Cool, N. Hansen and T. Kasper, Int. J. Mass Spectrom., 2008, 269, 210. [3] T.A. Cool, J. Wang, K. Nakajima, C. A. Taatjes and A. McIlroy, Int. J. Mass Spectrom., 2005, 247,18. [4] J. C. Robinson, N. E. Sveum and D. M. Neumark, J. Chem. Phys., 2003, 119, 5311. [5] T. A. Cool, K. Nakajima, T. A. Mostefaoui, F. Qi, A. Mcllroy, P. R. Westmoreland, M. E. Law, L. Poisson, D. S. Peterka and M. Ahmed, J. Chem. Phys., 2003, 119, 8356. [6] J. C. Robinson, N. E. Sveum and D. M. Neumark, Chem. Phys. Lett., 2004, 383, 601. [7] J. C. Person and P. P. Nicole, J. Chem. Phys., 1970, 53, 1767. [8] B. Yang and T. A. Cool et. al, unpublished. [9] J. Wang, B. Yang, T.A. Cool, N. Hansen and T. Kasper, Int. J. Mass Spectrom., 2008, 269, 210. 5

Table S2. Kinetic reaction mechanism for ethyl propanoate. Based on Metcalfe et al.33 with modifications made for reaction rates written in bold. Submechanism for epvd is new in this study. ethyl propanoate abbreviations Species Name Formula Ep ethyl propanoate CH3CH2(CO)OCH2CH3 ep3j ethyl propanoate radical 1 CH2CH2(CO)OCH2CH3 ep2j ethyl propanoate radical 2 CH3 CH(CO)OCH2CH3 epej ethyl propanoate radical 3 CH3CH2(CO)O CHCH3 epmj ethyl propanoate radical 4 CH3CH2(CO)OCH2 CH2 ee2j ethyl propanoate radical CH2(CO)OCH2CH3 mpmj methyl propanoate radical CH3CH2(CO)O CH2 ep2d ethyl propenoate CH2=CH(CO)OCH2CH3 epvd vinyl propanoate CH3CH2(CO)OCH=CH2 ep2dej ethyl propenoate radical 1 CH2=CH(CO)O CHCH3 ep2dmj ethyl propenoate radical 2 CH2=CH(CO)OCH2 CH2 ep2dvj ethyl propenoate radical 3 CH=CH(CO)OCH2CH3 epvd2j vinyl propanoate radical 1 CH3 CH(CO)OCH=CH2 epvd3j vinyl propanoate radical 2 CH2CH2(CO)OCH=CH2 epvdvj vinyl propanoate radical 3 CH3CH2(CO)OCH= CH Reaction A n Ea ep3j + h(+m) = ep(+m) 1.00E+14 0 0.00E+00 ep2j + h(+m) = ep(+m) 1.00E+14 0 0.00E+00 epej + h(+m) = ep(+m) 1.00E+14 0 0.00E+00 epmj + h(+m) = ep(+m) 1.00E+14 0 0.00E+00 ep(+m) = c2h5cooh + c2h4(+m) 6.00E+13 0 5.00E+04 ep(+m) = c2h5cooh + c2h4(+m) 1.60E+13 0 5.00E+04 ep(+m) = ee2j + ch3(+m) 5.73E+23 2.3 8.77E+04 ep(+m) = c2h5oco + c2h5(+m) 2.63E+27 3.2 9.47E+04 ep(+m) = c2h5co + c2h5o(+m) 1.65E+24 2 1.00E+05 ep(+m) = c2h5co2 + c2h5(+m) 5.73E+25 2.8 9.21E+04 ep(+m) = mpmj + ch3(+m) 3.39E+21 1.6 9.21E+04 ep + o2 = ep3j + ho2 3.00E+13 0 5.23E+04 ep + o2 = ep2j + ho2 2.00E+13 0 4.43E+04 ep + o2 = epej + ho2 2.00E+13 0 4.82E+04 ep + o2 = epmj + ho2 3.00E+13 0 5.23E+04 6

ep + h = ep3j + h2 1.33E+06 2.54 6.76E+03 ep + h = ep2j + h2 5.04E+13 0 7.30E+03 ep + h = epej + h2 3.25E+05 2.4 2.58E+03 ep + h = epmj + h2 1.88E+05 2.8 6.28E+03 ep + h = ep3j + h2 6.60E+05 2.54 6.76E+03 ep + h = ep2j + h2 2.52E+14 0 7.30E+03 ep + h = epej + h2 1.20E+06 2.4 2.58E+03 ep + h = epmj + h2 6.66E+05 2.8 6.28E+03 ep + o = ep3j + oh 1.96E+06 2.43 4.75E+03 ep + o = ep2j + oh 4.40E+12 0 3.28E+03 ep + o = epej + oh 2.81E+13 0 5.20E+03 ep + o = epmj + oh 1.03E+14 0 7.88E+03 ep + o = ep3j + oh 9.81E+05 2.43 4.75E+03 ep + o = ep2j + oh 2.20E+13 0 3.28E+03 ep + o = epej + oh 7.66E+05 2.41 1.14E+03 ep + o = epmj + oh 9.81E+05 2.43 4.75E+03 ep + oh = ep3j + h2o 1.06E+10 0.97 1.59E+03 ep + oh = ep2j + h2o 2.29E+10 0.51 6.30E+01 ep + oh = epej + h2o 2.29E+10 0.51 6.30E+01 ep + oh = epmj + h2o 1.05E+10 0.97 1.59E+03 ep + oh = ep3j + h2o 5.28E+09 0.97 1.59E+03 ep + oh = ep2j + h2o 1.15E+11 0.51 6.30E+01 ep + oh = epej + h2o 1.15E+11 0.51 6.30E+01 ep + oh = epmj + h2o 5.28E+09 0.97 1.59E+03 ep + ch3 = ep3j + ch4 4.53E 01 3.65 7.15E+03 ep + ch3 = ep2j + ch4 2.00E+11 0 7.90E+03 ep + ch3 = epej + ch4 1.20E 09 6.36 8.93E+02 ep + ch3 = epmj + ch4 4.53E 01 3.65 7.15E+03 ep + ho2 = ep3j + h2o2 2.38E+04 2.55 1.65E+04 ep + ho2 = ep2j + h2o2 4.32E+12 0 1.44E+04 ep + ho2 = epej + h2o2 7.22E+03 2.55 1.05E+04 ep + ho2 = epmj + h2o2 2.38E+04 2.55 1.65E+04 ep + ho2 = ep3j + h2o2 2.38E+04 2.55 1.65E+04 ep + ho2 = ep2j + h2o2 2.16E+12 0 1.44E+04 7

ep + ho2 = epej + h2o2 3.61E+03 2.55 1.05E+04 ep + ho2 = epmj + h2o2 2.38E+04 2.55 1.65E+04 ep + ch3o2 = ep3j + ch3o2h 2.38E+04 2.55 1.65E+04 ep + ch3o2 = ep2j + ch3o2h 4.32E+12 0 1.44E+04 ep + ch3o2 = epej + ch3o2h 7.22E+03 2.55 1.05E+04 ep + ch3o2 = epmj + ch3o2h 2.38E+04 2.55 1.65E+04 ep + c2h5 = ep3j + c2h6 4.52E 01 3.65 9.14E+03 ep + c2h5 = ep2j + c2h6 2.00E+11 0 7.90E+03 ep + c2h5 = epej + c2h6 1.08E+00 3.46 5.96E+03 ep + c2h5 = epmj + c2h6 4.52E 01 3.65 9.14E+03 ep + c2h3 = ep3j + c2h4 3.02E+02 3.3 1.05E+04 ep + c2h3 = ep2j + c2h4 4.00E+11 0 1.43E+04 ep + c2h3 = epej + c2h4 1.81E+00 3.46 2.61E+03 ep + c2h3 = epmj + c2h4 3.02E+02 3.3 1.05E+04 ep + ch3o = ep3j + ch3oh 2.17E+11 0 6.46E+03 ep + ch3o = ep2j + ch3oh 3.80E+10 0 2.80E+03 ep + ch3o = epej + ch3oh 4.58E+10 0 2.87E+03 ep + ch3o = epmj + ch3oh 2.17E+11 0 6.46E+03 ep3j = c2h4 + c2h5oco 8.83E+15 0.7 3.56E+04 ep2d + h = ep3j 1.00E+13 0 2.90E+03 ep2j = ch3chco + c2h5o 2.79E+22 2.3 4.57E+04 ep2j = ep2d + h 1.32E+14 0.2 4.09E+04 epej = ch3cho + c2h5co 1.13E+21 1.7 4.06E+04 epvd + h = epej 1.00E+13 0 2.90E+03 epvd + h = epmj 1.00E+13 0 2.90E+03 epmj = c2h4 + c2h5co2 2.33E+14 0.2 3.30E+04 ep2d = c2h3 + c2h5oco 4.28E+22 1.7 1.08E+05 ep2d = c2h3co + c2h5o 1.38E+23 1.8 9.02E+04 ep2d = mp2dmj + ch3 2.52E+20 1 9.22E+04 ep2d + o2 = ep2dej + ho2 2.00E+13 0 4.82E+04 ep2d + o2 = ep2dmj + ho2 3.00E+13 0 5.23E+04 8

ep2d + o2 = ep2dvj + ho2 1.40E+12 0 6.07E+04 ep2d + h = ep2dej + h2 1.20E+06 2.4 2.58E+03 ep2d + h = ep2dmj + h2 6.66E+05 2.54 6.76E+03 ep2d + h = ep2dvj + h2 4.05E+05 2.5 9.79E+03 ep2d + o = ep2dej + oh 7.66E+05 2.41 1.14E+03 ep2d + o = ep2dmj + oh 9.81E+05 2.43 4.75E+03 ep2d + o = ep2dvj + oh 6.03E+10 0.7 7.63E+03 ep2d + oh = ep2dej + h2o 1.15E+11 0.51 6.30E+01 ep2d + oh = ep2dmj + h2o 5.28E+09 0.97 1.59E+03 ep2d + oh = ep2dvj + h2o 1.11E+06 2 1.45E+03 ep2d + ch3 = ep2dej + ch4 1.20E 09 6.36 8.93E+02 ep2d + ch3 = ep2dmj + ch4 4.53E 01 3.65 7.15E+03 ep2d + ch3 = ep2dvj + ch4 8.40E 01 3.5 1.17E+04 ep2d + ho2 = ep2dej + h2o2 7.22E+03 2.55 1.05E+04 ep2d + ho2 = ep2dmj + h2o2 2.38E+04 2.55 1.65E+04 ep2d + ho2 = ep2dvj + h2o2 3.00E+09 0 9.93E+03 ep2d + ch3o2 = ep2dej + ch2o2h 7.22E+03 2.55 1.05E+04 ep2d + ch3o2 = ep2dmj + ch3o2h 2.38E+04 2.55 1.65E+04 ep2d + ch3o2 = ep2dvj + ch3o2h ep2d + c2h5 = ep2dej + c2h6 1.08E+00 3.46 5.96E+03 ep2d + c2h5 = ep2dmj + c2h6 4.52E 01 3.65 9.14E+03 ep2d + c2h5 = ep2dvj + c2h6 1.00E+11 0 9.80E+03 ep2d + c2h3 = ep2dej + c2h4 1.81E+00 3.46 2.61E+03 ep2d + c2h3 = ep2dmj + c2h4 3.02E+02 3.3 1.05E+04 ep2d + c2h3 = ep2dvj + c2h4 8.40E 01 3.5 9.68E+03 ep2d + ch3o = ep2dej + ch3oh 4.58E+10 0 2.87E+03 ep2d + ch3o = ep2dmj + ch3oh 2.17E+11 0 6.46E+03 ep2d + ch3o = ep2dvj + ch3oh 4.00E+01 2.9 8.61E+03 epvd + h = epvd2j + h2 2.52E+14 0 7.30E+03 epvd + h = epvd3j + h2 6.66E+05 2.54 6.76E+03 epvd + h = epvdvj + h2 4.05E+05 2.5 9.79E+03 9

epvd + o = epvd2j + oh 2.20E+13 0 3.28E+03 epvd + o = epvd3j + oh 9.81E+05 2.43 4.75E+03 epvd + o = epvdvj + oh 6.03E+10 0.7 7.63E+03 epvd + oh = epvd2j + h2o 1.15E+11 0.51 6.30E+01 epvd + oh = epvd3j + h2o 5.28E+09 0.97 1.59E+03 epvd + oh = epvdvj + h2o 1.11E+06 2 1.45E+03 epvd + ho2 = epvd2j + h2o2 4.32E+12 0 1.44E+04 epvd + ho2 = epvd3j + h2o2 2.38E+04 2.55 1.65E+04 epvd + ho2 = epvdvj + h2o2 3.00E+09 0 9.93E+03 epvd + ch3 = epvd2j + ch4 2.00E+11 0 7.90E+03 epvd + ch3 = epvd3j + ch4 4.53E 01 3.65 7.15E+03 epvd + ch3 = epvdvj + ch4 8.40E 01 3.5 1.17E+04 epvd + ch3o = epvd2j + ch3oh 3.80E+10 0 2.80E+03 epvd + ch3o = epvd3j + ch3oh 2.17E+11 0 6.46E+03 epvd + ch3o = epvdvj + ch3oh 4.00E+01 2.9 8.61E+03 epvd + c2h3 = epvd2j + c2h4 4.00E+11 0 1.43E+04 epvd + c2h3 = epvd3j + c2h4 3.02E+02 3.3 1.05E+04 epvd + c2h3 = epvdvj + c2h4 8.40E 01 3.5 9.68E+03 epvd + c2h5 = epvd2j + c2h6 2.00E+11 0 7.90E+03 epvd + c2h5 = epvd3j + c2h6 4.52E 01 3.65 9.14E+03 epvd + c2h5 = epvdvj + c2h6 1.00E+11 0 9.80E+03 epvd + ch3o2 = epvd2j + ch3o2h 4.32E+12 0 1.44E+04 epvd + ch3o2 = epvd3j + ch3o2h 2.38E+04 2.55 1.65E+04 epvd + ch3o2 = epvdvj + ch3o2h 3.00E+09 0 9.93E+03 epvd + o2 = epvd2j + ho2 2.00E+13 0 4.43E+04 epvd + o2 = epvd3j + ho2 3.00E+13 0 5.23E+04 epvd + o2 = epvdvj + ho2 1.40E+12 0 6.07E+04 ep2dej = ch3cho + ch2chco 2.42E+23 2.7 3.33E+04 ep2dmj = c2h4 + c2h3co2 1.50E+12 0.44 3.20E+04 ep2dvj = c2h2 + c2h5co2 1.00E+14 0 4.50E+04 epvd2j = ch3chco + ch2cho 1.00E+14 0 4.50E+04 epvd3j = c2h4 + c2h3co2 1.00E+14 0 4.50E+04 epvdvj = c2h2 + c2h5co2 1.00E+14 0 4.50E+04 10

c2h3co2 = c2h3 + co2 1.00E+13 0 1.00E+04 ee2j = c2hco + c2h5o 9.36E+19 1.9 5.64E+04 11

Table S3. Methyl isobutanoate mechanism, including submechanism for methyl methacrylate methyl isobutanoate abbreviations Species Name Formula mib methyl isobutanoate CH3CHCH3(CO)OCH3 mibpj methyl isobutanoate radical 1 CH2CHCH3(CO)OCH3 mibtj methyl isobutanoate radical 2 CH3 CCH3(CO)OCH3 mibmj methyl isobutanoate radical 3 CH3CHCH3(CO)O CH2 mp2j methyl propanoate radical 2 CH3 CH(CO)O/CH3 ocoic3h7 methyl isobutanoate radical CH3CHCH3(CO)O mmethac methyl methacrylate CH2=CCH3(CO)OCH3 mmethmj methyl methacrylate radical 1 CH2=CCH3(CO)O CH2 mmethvj methyl methacrylate radical 2 CH=CCH3(CO)OCH3 mmethpj methyl methacrylate radical 3 CH2=C CH2(CO)OCH3 Reaction A n Ea mibmj + h = mib 1.00E+14 0 0.00E+00 mibtj + h = mib 1.00E+14 0 0.00E+00 mibpj + h = mib 1.00E+14 0 0.00E+00 mp2j + ch3 = mib 1.00E+13 0 0.00E+00 ocoic3h7 + ch3 = mib 1.00E+13 0 0.00E+00 ch3o + ic3h7co = mib 8.00E+12 0 0.00E+00 ch3oco + ic3h7 = mib 8.00E+12 0 0.00E+00 mib + h = mibmj + h2 9.40E+04 2.8 6.28E+03 mib + h = mibtj + h2 3.62E+06 2.5 6.76E+03 mib + h = mibpj + h2 1.88E+05 2.8 6.28E+03 mib + oh = mibmj + h2o 5.28E+09 1 1.59E+03 mib + oh = mibtj + h2o 1.15E+11 0.5 6.30E+01 mib + oh = mibpj + h2o 1.06E+10 1 1.59E+03 mib + o = mibmj + oh 9.81E+05 2.4 4.75E+03 mib + o = mibtj + oh 3.94E+05 2.4 1.15E+03 mib + o = mibpj + oh 1.96E+06 2.4 4.75E+03 mib + ch3 = mibmj + ch4 4.53E 01 3.7 7.15E+03 12

mib + ch3 = mibtj + ch4 2.72E+00 3.7 7.15E+03 mib + ch3 = mibpj + ch4 9.06E 01 3.7 7.15E+03 mib + ho2 = mibmj + h2o2 2.38E+04 2.6 1.65E+04 mib + ho2 = mibtj + h2o2 7.22E+03 2.6 1.05E+04 mib + ho2 = mibpj + h2o2 4.76E+04 2.6 1.65E+04 mib + o2 = mibmj + ho2 3.00E+13 0 5.23E+04 mib + o2 = mibtj + ho2 4.08E+13 0 4.14E+04 mib + o2 = mibpj + ho2 6.00E+13 0 5.23E+04 mib + ch3o = mibmj + ch3oh 2.17E+11 0 6.46E+03 mib + ch3o = mibtj + ch3oh 3.80E+10 0 2.80E+03 mib + ch3o = mibpj + ch3oh 4.34E+11 0 6.46E+03 mib + ch3o2 = mibmj + ch3o2h 2.38E+04 2.6 1.65E+04 mib + ch3o2 = mibtj + ch3o2h 7.22E+03 2.6 1.05E+04 mib + ch3o2 = mibpj + ch3o2h 4.76E+04 2.6 1.65E+04 mib + c2h3 = mibmj + c2h4 3.02E+02 3.3 1.05E+04 mib + c2h3 = mibtj + c2h4 4.00E+11 0 1.43E+04 mib + c2h3 = mibpj + c2h4 6.03E+02 3.3 1.05E+04 mib + c2h5 = mibmj + c2h6 4.52E 01 3.7 9.14E+03 mib + c2h5 = mibtj + c2h6 2.00E+11 0 7.90E+03 mib + c2h5 = mibpj + c2h6 9.04E 01 3.7 9.14E+03 ch2o + ic3h7co = mibmj 1.00E+11 0 8.20E+03 ch3o + ic3h6co = mibtj 1.00E+11 0 8.20E+03 h + mmethac = mibtj 4.00E+10 0 2.90E+03 ch3 + mp2d = mibpj 1.00E+11 0 8.20E+03 ch3oco + c3h6 = mibpj 5.00E+11 0 8.20E+03 h + mmethac = mibpj 5.00E+11 0 2.90E+03 ic3h7 + co2 = ocoic3h7 1.00E+11 0 8.20E+03 mibtj + o2 = mmethac + ho2 3.00E 09 0 3.00E+03 mibpj + o2 = mmethac + ho2 3.00E 09 0 3.00E+03 mmethac + h = mmethmj + h2 6.66E+05 2.5 6.76E+03 mmethac + o = mmethmj + oh 9.81E+05 2.4 4.75E+03 13

mmethac + oh = mmethmj + h2o 5.28E+09 1 1.59E+03 mmethac + ho2 = mmethmj + h2o2 2.38E+04 2.6 1.65E+04 mmethac + ch3 = mmethmj + ch4 4.53E 01 3.7 7.15E+03 mmethac + ch3o = mmethmj + ch3oh 2.17E+11 0 6.46E+03 mmethac + ch3o2 = mmethmj + ch3o2h 2.38E+04 2.6 1.65E+04 mmethac + c2h3 = mmethmj + c2h4 3.02E+02 3.3 1.05E+04 mmethac + c2h5 = mmethmj + c2h6 4.52E 01 3.7 9.14E+03 mmethac + o2 = mmethmj + ho2 3.00E+13 0 5.23E+04 mmethac + h = mmethvj + h2 4.05E+05 2.5 9.79E+03 mmethac + o = mmethvj + oh 6.03E+10 0.7 7.63E+03 mmethac + oh = mmethvj + h2o 1.11E+06 2 1.45E+03 mmethac + ho2 = mmethvj + h2o2 3.00E+09 0 1.99E+04 mmethac + ch3 = mmethvj + ch4 8.40E 01 3.5 1.17E+04 mmethac + ch3o = mmethvj + ch3oh 4.00E+01 2.9 8.61E+03 mmethac + ch3o2 = mmethvj + ch3o2h 3.00E+09 0 9.93E+03 mmethac + c2h3 = mmethvj + c2h4 8.40E 01 3.5 9.68E+03 mmethac + c2h5 = mmethvj + c2h6 1.00E+11 0 9.80E+03 mmethac + o2 = mmethvj + ho2 1.40E+12 0 6.07E+04 mmethac + h = mmethpj + h2 6.66E+05 2.5 6.76E+03 mmethac + o = mmethpj + oh 9.81E+05 2.4 4.75E+03 mmethac + oh = mmethpj + h2o 5.28E+09 1 1.59E+03 mmethac + ho2 = mmethpj + h2o2 2.38E+04 2.6 1.65E+04 mmethac + ch3 = mmethpj + ch4 4.53E 01 3.7 7.15E+03 mmethac + ch3o = mmethpj + ch3oh 2.17E+11 0 6.46E+03 mmethac + ch3o2 = mmethpj + ch3o2h 2.38E+04 2.6 1.65E+04 mmethac + c2h3 = mmethpj + c2h4 3.02E+02 3.3 1.05E+04 mmethac + c2h5 = mmethpj + c2h6 4.52E 01 3.7 9.14E+03 mmethac + o2 = mmethpj + ho2 3.00E+13 0 5.23E+04 mmethac + oh = mp2j + ch2o 1.00E+11 0 4.00E+03 mmethac + oh = ch3coch3 + ch3oco 1.00E+11 0 4.00E+03 mmethac + o = ch3coch2 + ch3oco 1.00E+11 0 1.05E+03 mmethmj = ch2o + ic3h5co 1.00E+14 0 4.50E+04 mmethvj = c3h4 p + ch3oco 1.00E+14 0 4.50E+04 mmethpj = c3h4 a + ch3oco 1.00E+14 0 4.50E+04 mmethac = ic3h5co + ch3o 1.00E+16 0 7.10E+04 mmethac = c3h5 a + ch3oco 1.00E+16 0 7.10E+04 14

Table S4. Rate expressions for H atom abstraction reactions by OH, H, and HO 2 radicals in functional groups of importance in the present study. The three C 5 H 10 O 2 methyl esters are shown in bold type. Reactions with an asterisk * indicate the final values in cases where the reaction rates were modified. Final column shows reaction rate evaluated at 1000K. A n Ea rate (1000K) cal/mol cm 3 mol 1 s 1 R(CO)OCH3 methyl formate + OH 5.27E+09 0.97 1590 1.92E+12 methyl ethanoate + OH 5.27E+09 0.97 1590 1.92E+12 methyl propanoate + OH 5.27E+09 0.97 1590 1.92E+12 methyl butanoate + OH 7.02E+07 1.61 35 4.83E+12 methyl isobutanoate + OH 5.27E+09 0.97 1590 1.92E+12 methyl formate + H 6.66E+05 2.54 6756 9.26E+11 methyl ethanoate + H 9.40E+04 2.75 6280 7.09E+11 methyl propanoate + H 9.40E+04 2.75 6280 7.09E+11 methyl butanoate + H 1.95E+06 2.4 4471 3.26E+12 methyl isobutanoate + H 9.40E+04 2.75 6280 7.09E+11 methyl formate + HO2 2.38E+04 2.55 16490 2.64E+08 methyl ethanoate + HO2 4.04E+04 2.5 16690 2.87E+08 methyl propanoate + HO2 4.04E+04 2.5 16690 2.87E+08 methyl butanoate + HO2 1.23E+04 2.6 13910 7.07E+08 methyl isobutanoate + HO2 2.38E+04 2.55 16490 2.64E+08 CH3(CO)OR methyl acetate + OH 1.40E+10 0.51 63 4.60E+11 ethyl acetate + OH 1.40E+10 0.51 63 4.60E+11 methyl acetate + H 1.50E+05 2.4 2583 6.48E+11 ethyl acetate + H 1.50E+05 2.4 2583 6.48E+11 methyl acetate + HO2 9.00E+02 2.55 10532 2.01E+08 ethyl acetate + HO2 9.00E+02 2.55 10532 2.01E+08 CH3CH2(CO)OR c2h5cooh + OH 5.28E+09 0.97 1586 1.93E+12 methyl propanoate + OH 5.28E+09 0.97 1586 1.93E+12 15

* ethyl propanoate + OH 5.28E+10 0.97 1586 1.93E+13 ethyl propanoate + OH 1.06E+10 0.97 1586 3.88E+12 c2h5cooh + H 5.28E+09 0.97 1586 1.93E+12 methyl propanoate + H 6.66E+06 2.54 6756 9.26E+12 ethyl propanoate + H 6.66E+05 2.54 6756 9.26E+11 * ethyl propanoate + H 1.33E+06 2.54 6756 1.85E+12 c2h5cooh + HO2 2.38E+04 2.55 16490 2.64E+08 methyl propanoate + HO2 2.38E+04 2.55 16490 2.64E+08 ethyl propanoate + HO2 2.38E+04 2.55 16490 2.64E+08 CH3CH2(CO)OR c2h5cooh + OH 1.15E+11 0.51 63 3.78E+12 methyl propanoate + OH 1.15E+11 0.51 63 3.78E+12 ethyl propanoate + OH 1.15E+11 0.51 63 3.78E+12 * ethyl propanoate + OH 2.29E+10 0.51 63 7.52E+11 c2h5cooh + H 2.54E+14 0 7300 6.45E+12 methyl propanoate + H 6.66E+06 2.54 6756 9.26E+12 ethyl propanoate + H 2.52E+14 0 7300 6.40E+12 * ethyl propanoate + H 5.04E+13 0 7300 1.28E+12 c2h5cooh + HO2 4.32E+12 0 14400 3.08E+09 methyl propanoate + HO2 2.16E+12 0 14400 1.54E+09 ethyl propanoate + HO2 4.32E+12 0 14400 3.08E+09 CH3CHCH3(CO)OR methyl isobutanoate + OH 2.93E+04 2.53 1659 2.63E+12 isobutane + OH 2.93E+04 2.53 1659 2.63E+12 2 methyl butane + OH 5.73E+10 0.51 63 1.88E+12 methyl isobutanoate + H 6.02E+05 2.54 2583 6.84E+12 isobutane + H 6.02E+05 2.54 2583 6.84E+12 2 methyl butane + H 6.02E+05 2.54 2583 6.84E+12 methyl isobutanoate + HO2 7.22E+03 2.55 10530 1.61E+09 isobutane + HO2 2.80E+12 0 16010 8.87E+08 2 methyl butane + HO2 2.80E+12 0 16010 8.87E+08 16

CH3CHCH3(CO)OR methyl isobutanoate + OH 1.06E+10 0.97 1586 3.88E+12 isobutane + OH 6.65E+04 2.67 1689 1.59E+13 2 methyl butane + OH 1.05E+10 0.97 1590 3.85E+12 methyl isobutanoate + H 1.88E+05 2.75 6280 1.42E+12 isobutane + H 1.81E+06 2.54 6756 2.52E+12 2 methyl butane + H 1.21E+06 2.54 6756 1.68E+12 methyl isobutanoate + HO2 4.76E+04 2.55 16490 5.29E+08 isobutane + HO2 6.12E+01 3.59 17160 6.40E+08 2 methyl butane + HO2 1.68E+13 0 20440 5.73E+08 R(CO)OCH2CH3 ethyl formate + OH 1.05E+10 0.97 1586 3.84E+12 ethyl acetate + OH 1.05E+10 0.97 1586 3.86E+12 ethyl propanoate + OH 5.28E+09 0.97 1586 1.93E+12 * ethyl propanoate + OH 1.06E+10 0.97 1586 3.88E+12 ethyl formate + H 1.88E+05 2.75 6280 1.42E+12 ethyl acetate + H 6.66E+05 2.54 6756 9.26E+11 ethyl propanoate + H 6.66E+05 2.54 6756 9.26E+11 * ethyl propanoate + H 1.88E+05 2.8 6280 2.00E+12 ethyl formate + HO2 1.68E+13 0 20430 5.75E+08 ethyl acetate + HO2 2.38E+04 2.55 16490 2.64E+08 ethyl propanoate + HO2 2.38E+04 2.55 16490 2.64E+08 R(CO)OCH2CH3 ethyl formate + OH 1.16E+07 1.61 35 7.98E+11 ethyl acetate + OH 2.29E+10 0.51 63 7.52E+11 ethyl propanoate + OH 1.15E+11 0.51 63 3.78E+12 * ethyl propanoate + OH 1.16E+07 1.61 35 7.98E+11 ethyl formate + H 3.25E+05 2.4 4471 5.43E+11 ethyl acetate + H 1.20E+05 2.4 2583 5.18E+11 ethyl propanoate + H 1.20E+06 2.4 2583 5.20E+12 * ethyl propanoate + H 3.25E+05 2.4 2583 1.40E+12 ethyl formate + HO2 5.60E+12 0 17700 7.58E+08 17

ethyl acetate + HO2 7.22E+03 2.55 10530 1.61E+09 ethyl propanoate + HO2 7.22E+03 2.55 10530 1.61E+09 * ethyl propanoate + HO2 3.61E+03 2.5 10530 5.70E+08 CH3CH2CH2(CO)OCH3 methyl butanoate + OH 1.15E+11 0.51 63 3.78E+12 * methyl butanoate + H 2.00E+05 2.4 2583 8.64E+11 methyl butanoate + H 6.00E+05 2.4 2583 2.59E+12 methyl butanoate + HO2 1.23E+04 2.6 13910 7.07E+08 CH3CH2CH2(CO)OCH3 methyl butanoate OH 4.68E+07 1.61 35 3.22E+12 methyl butanoate + H 1.30E+06 2.4 4471 2.17E+12 methyl butanoate + HO2 8.19E+03 2.6 13910 4.71E+08 CH3CH2CH2(CO)OCH3 methyl butanoate + OH 5.28E+09 0.97 1586 1.93E+12 methyl butanoate + H 6.66E+05 2.54 6756 9.26E+11 methyl butanoate + HO2 2.02E+04 2.55 16490 2.24E+08 18

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